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Patented Sept. 29, 1953 UNITED STATES PA -nut 2, 53,927 nnrunoorcurc AZO-DYESTUFF charles' Graena'cher Biehen, and Heinrich Bruen-gger'--and =-Adlf- Emil Siegrist, Basel, Switzerland, assign'ors tojCiba Limited, Basel;

P Switzerland a Swiss firm I OH,

inwhich R1 represents a cyclic radical; condensed onto the benzene ring at the positions indicated byithevalence bonds; and R represents the radi= oalof a diaz'o component free' from acylamino groups-With 'two molecular proportions of an acid monohalide-of the-generalformula fr? 1/ o-0-Y in which A represents a S-membered heterocyclic ring consisting of 4 carbon atoms bound together by conjugate double bonds and one sulfur atom or advantageousl one oxygen atom, and one Y representsa hydroxylgroup-.andthe other Y a halogenatom. I 't ,7 i A largehnumber of. thedyestufifs of the above formula are known, especially.fasi'pigrnents: producedlro n, the fiber. 'Asis knownthedyestufis can also be prepared in substance in a siniple manner by coupling a diaz'o-com'pound free from' acylamino groups and groups impa'rting solubility with a coupling component which contains the atomic grouping "CO NH ATYl As diazo-compounds there may be used diazotized bases such as are customarily used for the manufacture of ice colors-for example, the diazocompounds of 3-chloro-1-aminobenzene, 2:5-di- -chloro -'-1"- aminobenzene, 2 trifiuoromethyl =4- chloro 1 aminobenzene, 2, oh lor'o "5 trifluoromethyl-l-aminobenzene', 2-ethylsulfone-5- trifluoromethyl 1 aminobenzeneg azfie di-i ttri fluorcmethyl) l aminob'en zen'e, 2 nitr'o -:1- aminobenzene, 2 nitro-4chloro l aininobenzene, 2 nitro' methyl 1 amin'obenzeney2lnitro- 4 methoxy 1 aminobenzene;*2 methoxy 5 nitro 1 --aminobenzene- 2-'- methyl :4 L chloro- 1 14 aminobenzene, 2'---=m hoxy "5'=.chloro =11- -ami-nobenzene; 3:2 '--'di-methyl-'*- 4 amino 111- azobenze'neand' l'-am-inonaphthalen 7.

n lflnlfiii'iianon July 13, 1950, Seria n Swituerland July 22, 1949 *2 As coupling components there may be used,,for exampleQbOmpo-unrispf the general formulae NH w and especially those of the generalformula and above all those of the general formula The aryl radical may be, for example, a napthalene radical or a radical of the benzene series such, for example, asiiphenyl, 2-methyl- 1 phenyl, 2-methoxyi-iphe nyl; 4-chloro-2-methylphenyl, 2 5-dimethoxy-4-cholor-phenyl, 2 l-dimethoxy-5.-"cholorephenyl; Z-methYkts-Lmet Q Y- 'phenyl'andfthe likexa-:': 1 "gs-f '1 y 1 A's acid im onohalideswoit 'abovewmentioned formula w v A H.

-'so'-Y v there comes in consideration for use in the present process the monohalides, for example, the mono-bromides and above'all the monochlorides, of furane-2-carboxylic acid-3-sulfonic acid, of azeedicholoroiurane-hcarboxylic acid-5-sulfonic acid, "of .5-chloroiurahe-2,-'carbOXylic acid=3+sulfonic acid, of 5,-bromo-f urane-2-carbo xylic acid.- 3. ,-sulfonic acidjand especially of thiophene-2- c'arboxylic ,aci'df-5-slulfonic acidlor advantageously.of.furane-2-lqarboxylic acid-5-sulf0nic acid.

There. may beluseld, as. acid, halide for'this 'inveritionfleitherj a "sulfonic acid halide-carboxylic ac'i'd foft the l constitution yew-H logen A T-0H or a vcarboxylic -acid,;halide-sulfonic acidv ;of. the constitution. v a I I v l v, y, t. Q/s/OFOH Q..Q-Halogen x-rFor. thespresentsinventionthere are principal- 1yv 'suitablesthose oid shalidesl of; the --above kind which contain the group -CO-Halogen, especially the group --COC1, wherein the -SO3H group also capable of forming an acid halide group is not converted into an --SOz-Halogen group. The acid halides of the general formula SOz-Cl which are also suitable for the instant process may be obtained, for example, by reacting a carboxylic acid of the formula with chlorosulfonic acid. The preparation is advantageously carried out by introducing the acid in question at room temperature into an excess of chlorosulfonic acid, then allowing the mixture to react for a short time at a higher temperature, for example, at about 100 C., cooling the mixture and pouring it on to ice, taking up the resulting acid chloride in an organic solvent, for example, in ether, dehydrating the resulting solution, and finally distilling ofi the solvent.

Acid halides of the general formula C O-Halogen ma be prepared, for example, by sulfonating an acid halide of the constitution C O-Halogen The sulfonation may be conducted, for example, at a low temperature by means of sulfur trioxide in liquid sulfur dioxide or with special advantage in methylene chloride (CH2C12).

An especially advantageous method for preparing acid halides of the last mentioned formula consists in reacting an acid of the formula SOaH COOH especially furane-2-carboxylic acid-fi-sulfonic acid with the aid of an aromatic sulfonic acid halide such as benzene sulfonic acid chloride, para-toluene sulfonic acid bromide or para-toluene sulfonic acid chloride, or, with special advantage, with the aid of phosgene. As a rule it is desirable to conduct this reaction in the presence of a tertiary organic base, for example, trimethylamine, triethylamine, N-methyl-morpholine or advantageously pyridine. When the reaction is conducted in the absence of pyridine and in the presence of trimethylamine or triethylamine, it is generally of advantage in order to obtain a smooth reaction to work with the addition of an inert organic solvent such as benzene, chlorobenzene, ortho-dichlorobenzene, l :2 :4-trichlorobenzene, nitrobenzene, dioxane, etc. These methods also have the advantage that the mixture so obtained, which contains the desired carboxylic acid halide-sulfonic acid, can be used directly for reaction with the dyestuiis in accordance with the present process.

Such mixtures are advantageously prepared by first introducing the acid of the formula sOaH COOH into pyridine, and then adding at a moderately raised temperature, for example, at 30-40 C., the acid halide (for example, para-toluene sulfonic acid chloride), or introducing gaseous phosgene.

An especially valuable acylating agent is obtained by adding to the mixture obtained as described above an additional tertiary base which is stronger than pyridine, for example, trimethylamine or advantageously triethylamine. Thus, for example, the dibasic acid of the formula SOaH may be mixed with pyridine, then the acid halide is added or phosgene is introduced, and finally triethylamine is also added. Alternatively, such dibasic acid may be mixed with an inert organic solvent, a suitable tertiary base (advantageously triethylamine) and the dyestufi, and then the acid halide is added to this mixture or phosgene is introduced into it. Finally, an acid halide of the formula first given above, such, for example, as furaneor thiophene-Z-carboxylic acid chloride-S-sulfonic acid (prepared, for example, by one of the other methods described above), may be mixed with the addition of an inert organic solvent with triethylamine and the dyestuif, and the acylation of the dyestuii" is then carried out at a raised temperature. By all these methods the radical SOIH is very easily introduced twice into the dyestuff molecule. Thus, on the one hand, the hydroxyl group of the radical of the coupling component is esterified and, on the other, a second acyl radical enters into the -NH-Acyl group. Even when an acid halide of the formula S O z-Halogen is used for the acylation there is obtained an acyl derivative of the above constitution and not one containing the acyl radical COOH [see also Ruggli, Helvetica Chimica Acta, vol. 24, page 197 (1941)].

The dyestufi derivatives so obtained are generally easily soluble in water. It is easy to establish that no starting material is still present in the reaction mixture by ascertaining whether a test portion diluted with acidulated water contains any water-insoluble dyestufi.

The reaction mixture may be worked up, for example, by pouring the whole, after cooling, into a dilute mineral acid, for example, sulfuric acid, precipitating the dyestuil from the acid solution by the addition of sodium chloride, separating o ta nabl xnt e.

present process are new."""Aecordiiig"to presenfi general knowledge (see Helvetica Chimica Acta, vol. 24, Fasc. Extraord, pages 50-57%. they correspond tothe general formula in v lqhfi r re n s yc cvr diwi c d n eq e t b n ene, r dic i t e n er i d e cated fiz represents the radical of a dialzo gcom: tent. tree r m a y mi s ou s n A r 12:

entw -me b eq eroc c ie ring on i ts-v.4

sp erbqn, a m b und be th nb s n: i set? ge ub e b nds A a d 9 s l u 9 v@ y m e ew-A ar r m t e e u li diwte e.

in thip ula l heyl a n" i u a int 'ojthe' original I dyestuffs.

Owing tothese properties thenew dyestuff derivatives obtainable the' present process are ei' valuable products, which are especially suitableforthe production of textile dyeings, for

example fdulard dyeingsgand for use 'in pence Very'valuable results are obtained by treating with alkali s, preferably ammonia," prints pro:

duoed inj kno'vvn" manner by'means of acid to neutral printing pastes, 'vvhioh contain a "dyestuff derivative obtained by the "present process.- This treatment with alkali is advantageously carried out with Weak iancidilute alkalis, if desired, yvith gaseous ammonia. The present invention also includes such ap'rinting prooess,

Dyestufiderivatives r a; f constitiition similar to those fof the present invention are -de'scrillged' in"Br itish Patent No. '480,35g. ndwverfprint-" ing withthese known dyestuff derivatives "en-1- tails certain difficulties, since the hydrolysis of those products generally requires a eert'ain "time. Ifi't isattemptedinthe "case of prints produced" with these known dyestuffderivatives to by drolyz'e them, for example, hytreatment'with al-' kali s', the hydrolysis is frequently's'o 'slo'w'"that there is sufficient time for thejsoluble' dyestufi derivative to be dissolved from" the 'fi'b'er In" this manner not" only are the parts originally printed'weakened in"dyeing 's'trength, but the dy'estuff derivative removed' by 'gii'ssol'utioziffre j quentlyoolors the unprinted'parts. "By'the pfoef ess of British'Pa-tent No'. 512,664 it issought to" overcome this disadvantage of the known prod 15 it'is 'ex'eaor am at acids,

sed; has

lli er. s'

bse en raetbr'y fol owing hpeggp'rf n ineiongm gs vvi'ngto their i'esis rice ye'ing an printing wool,

0 nown dyestuif derivatives of s 30 British ent No 4801358 7r""not alvva 'aa short nreatmnt c'olddil iite solution '0:

" 'iryi'ngout thehydrolysis aciu mafiim afia raised temperature, "for exampl, at 95309- In' this waytpere are obtained" valuable dyeings distinguished rincipa11y"-'=by Tli following examples illustrate the inven aminonaphthalene ancl gz' hydroxy 3 naphthoylaminohbenzene are added, and the redye'spujri ighgift rapidly dissolves and after. a short not: the initial 'v'iolet-red' coloration of' the reaction mixture is-then soluble in water to a clear solution. The reaction mixture is cooled to room temperature, and then stirred into a mixture of 150 parts of water and 21 parts of concentrated sulfuric acid, 10 parts of sodium chloride are added, and the whole is heated to 40-50 0., whereupon the reaction product precipitates well in the form of a resinous deposit. After pouring off the acid pyridine liquor, the residue is dissolved in 100 parts of water while heating to 40-50 C., and it is again precipitated in a resinous form by means of -10 parts of sodium chloride at 40-50 C., and the latter is separated from the salt solution and dried in vacuo at 40-50 C. The reaction product is a brown powder which dissolves easily in water to give a clear solution having a brown coloration, and is rapidly hydrolyzed by means of dilute alkalis, especially ammonia, to the insoluble initial bordeaux red pigment. As starting material there is advantageously used the dry furane-Z-carboxylic acid-5-sulfonic acid free from water of crystallization and obtainable in the following manner:

Into a powerful kneading apparatus, which can be hermetically closed, are introduced 1121 parts of dry finely powdered furane-Z-carboxylic acid and 1680 parts of methylene chloride which has been dried over sodium sulfate. The whole is thoroughly stirred for /;-1 hour, and then the mixture is cooled to -15 C. In the course of 3 hours 840 parts of sulfur trioxide are slowly introduced by distillation into the suspension of furane-Z-carboxylic acid while continuously stirring, the temperature being maintained through out between 10 and C. The reaction mass becomes noticeably more fluid and acquires a dark brown color. When about 600-620 parts of sulfur trioxide have been introduced by distillation, the furane-2-carboxylic acid-5-sulfonic acid separates from the thinly liquid suspension in the form of a mass which becomes progressively more viscous, up to the end of the introduction of sulfur trioxide. The honey-like mass is stirred for a further 11 /2 hours while the temperature is maintained at 10 to 15 C. throughout. A slow crystallization of furane-2-carboxylic acid-5- sulfonic acid can then be observed, and the crystals agglomerate to form large slag-like structures. After further stirring at 10 to 15 0., these slag-like structures are disintegrated and after stirring for /g-l hour the furane-z-carboxylic acid-5-sulfonic acid is obtained in the form of a dark green finely pulverized suspension. The whole is filtered with suction, while excluding moisture, in order to remove methylene chloride, and the furane-2-carboxylic acid-S-sulfonic acid is completely dried in vacuo at room temperature. (The methylene chloride may also be removed by distillation in vacuo at room temperature.) Furane-2-carboxylic acid-S-sulfonic acid is obtained in quantitative yield (calculated on the initial furane-Z-carboxylic acid) in the form of a pale olive-green powder which is free from water of crystallization and is stable when stored with complete exclusion of moisture. It only becomes darker. The product decomposes very rapidly in the atmosphere.

Example 2 6.8 parts of the anhydrous disodium salt of furane-2-carboxylic aoid-5-sulfonic acid are mixed with 30 parts by volume of dry pyridine, while stirring, 6.3 parts of para-toluene sulfochloride are added, and then 3.2 parts of the azo dyestuff from diazotized 1 aminonaphthalene and (2' hydroxy 3 naphthoylamino) benzene are added. The reaction mixture is heated to 90-95 C. while stirring, and after the reaction has proceeded for hour a test portion is soluble in water to give a clear solution. The acylation product is recovered in a manner corresponding to that described in Example 1, and the resulting brown reaction product is identical with the product of that example.

Example 3 18.6 parts of sodium furane-2-oarboxylio acid- 5-sulfonate free from water of crystallization (CsHsOsSNa; prepared as described by Hill and Palmer, American Chemical Journal, vol. 10, page 373 [1888]) are mixed with 120 parts by volume of dry pyridine at YO- C., while stirring. 10 parts of the azo dyestuff from diazotized 3-ohloro-l-aminobenzene and 1-(2'-hydroxy-3'- naphthoylamino)-2-methylbenzene are added, and 8.6 parts of phosgene are introduced in the course of 1 hours in the form of a gaseous stream, the temperature being maintained throughout at 70-75 C. The red crystalline magma, consisting of the acid sodium salt of 5- sulfo-2-furane-carboxylic acid and the dyestuff pigment, becomes slowly darker, and both components slowly dissolve. After the addition of the phosgene the whole is maintained for a further 30-60 minutes at TO-75 C. until the pigment dyestuff has completely dissolved with a brown coloration, and a test portion of the reaction mixture is soluble in water to give a clear solution. After cooling to room temperature, the whole is stirred into a cold mixture of 450 parts of Water and 63 parts of concentrated sulfuric acid. By the addition of 45 parts of sodium chloride the reaction product is salted out in the form of an oily mass which agglomerates upon heating to 40-45" C. so that, after cooling, the sulfuric acid-pyridine liquor can be separated satisfactorily. The reaction product is dissolved with 500 parts of water and 7 parts by volume of acetic acid of 10 per cent strength and is again salted out with 70 parts of sodium chloride. After being dried at 40-50" C. in vacuo, the reaction product is an orange-brown powder which dissolves easily in water to give a clear solution having an orange-brown coloration, and after the addition of a dilute alkali immediately hydrolyzes to the insoluble initial pigment.

Example 4 19.2 parts of furane-Z-carboxylic acid-S-sulfonic acid are dissolved in parts by volume of dry pyridine, while stirring, and 18.6 parts of the azo dyestuff from diazotized 2:5-dichlorol-aminobenzene and l-(2-hydroxy-3'naphthoylamino) -2-methoxybenzene are added. 1.9 parts of phosgene are then introduced into the mixture at 30-40 C. in the course of about 2 hours, and then the mixture is heated to 90-95 C. After a short period of reaction (about hour) the dyestuif pigment dissolves, and a test portion of the reaction mixture dissolves in water to give a clear solution. The reaction mixture is cooled. to room temperature, and stirred into a mixture of 350 parts of water and 40 parts of concentrated sulfuric acid. 25 parts of sodium chloride are added and the whole is heated to 40-50 C., whereupon the reaction product separates well in the form of a resinous deposit. After pouring off the acid pyridine liquor, the

5 residue is dissolved in 400 parts of water while 11 separated by hydrolysis with a dilute alkali in the form of the insoluble black-brown initial pigment.

Example 9 4.2 parts of furane-2-carboxylic acid-5-sulfonic acid chloride are dissolved in 30 parts by volume of dry pyridine while gently heating, 2.1 parts of the azo dyestuff from diazotized l-aminonaphthalene and (2-hydroxy-3'-naphthoy1- amino) -benzene are added, and the reaction mixture is then heated to 90-95 C. while stirring. After a reaction period of about /2 hour, the initial bordeaux pigment will have dissolved and a test portion of the reaction mixture will have become soluble in water to give a clear solution having a brown coloration. The reaction mixture is cooled to room temperature and then stirred into a mixture of 120 parts of water and parts of concentrated sulfuric acid, 7 parts of sodium chloride are added and the whole is heated to 40-45 C., whereupon the reaction product precipitates well in the form of a resinous deposit. After pouring off the acid pyridine liquor, the residue is dissolved in 100 parts of water while heating to 40-50" C., the product is salted out with 10 parts of sodium chloride, and the precipitated reaction product is separated. The reaction product is a brownred powder which dissolves easily in water to give a clear solution having a brown-red coloration, and can be hydrolyzed rapidly by means of dilute alkalis to form the initial insoluble bordeaux pigment. The furane-2-carboxylic acid- 5-sulfonic acid chloride may be prepared in the followin manner:

parts of furane-2-oarboxylic acid are introduced at room temperature, while stirring into 80 parts of chlorosulfonic acid. The whole is then heated to 100 C. in the course of minutes and maintained at that temperature for 2 hours. After cooling, the whole is poured on to 300 parts of ice, extracted with 100 parts of ether, the ethereal solution is dehydrated with anhydrous sodium sulfate, and the ether is distilled leaving behind furane-2-carboxylic acid-5-sulfonic acid chloride.

Example 10 7.3 parts of furane-Z-carboxylic acid chloride- 5-sulfonic acid are dissolved in 30 parts by volume of dry pyridine while stirring, 2.1 parts of the azo dyestuif from diazotized l-aminonapthalene and (2 -hydroxy-3-naphthoylamino) -benzene are added, and the reaction mixture is then heated to 90-95 C. After a reaction period of about V hour a test portion of the reaction mixture will have become soluble in water to give a clear solution. The product obtained by working up in the usual manner corresponds to the product of Example 9.

The furane-2-carboxylic acid chloride-5-sulfonic acid may be prepared in the following manner:

Into a flask fitted with stirring mechanism 26 parts of furane-2-carboxylic acid chloride are dissolved in 26 parts of methylene chloride while stirring, and the solution is then cooled to 10 C. A solution of 16.5 parts of sulfur trioxide in 24 parts of methylene chloride are then introduced dropwise in the course of 20 minutes while stirring and maintaining the temperature at -10 C. The whole is further stirred for 30 minutes, the temperature in the flask being allowed to rise to 0 C. The methylene chloride is distilled at room temperature leaving behind a brown reaction product, which is then dried in vacuo at room temperature overnight. The furane-Z-carboxylic acid chloride-5-sulfonic acid is obtained in the form of a brown viscous product.

Example 11 13 parts of the anhydrous disodium salt of 5- chlorofurane-Z-carboxylic acid-3-sulfonic acid (prepared as described by Hill and Hendrixson, American Chemical Journal, vol. 15, page 151 [1893]) are mixed with 60 parts by volume of dry pyridine while stirring, 9.2 parts of para-toluene sulfochloride are added, and then 5.0 parts of the azo dyestufi from diazotized 3-chloro-l-aminobenzene and 1- (2-hydroxy-3'-naphthoylamino) 2-methylbenzene are introduced. The reaction mixture is heated to 75-80 C. while stirring, and after hour a test portion is soluble in water to give a clear solution. The reaction mixture is cooled to room temperature, then stirred into a mixture of 250 parts of water and 32 parts of concentrated sulfuric acid, 30 parts of sodium chloride are added, and the whole is heated to -50 C., whereupon the reaction product separates well in the form of a resinous deposit. After pouring off the acid pyridine liquor, the residue is dissolved in 250 parts of water while heating at 40-50" C., the product is salted out with 30 parts of sodium chloride at 40-50 C., the salt solution is separated, and the reaction product is dried in vacuo at 40-50 C. The orange-brown product, which is soluble in water to give a clear solution, yields the initial insoluble pigment upon hydrolysis with dilute alkalis.

Example 12 benzene and 1-(2-hydroxy-3'-naphthoylamino) 2-methylbenzene are introduced. The reaction mixture is heated to 70-75 C. while stirring, and after hour a test portion is soluble in water to give a clear solution. The reaction mixture is cooled to room temperature and worked up in exactly the same manner as is described in Example 11. The orange-brown product, which dissolves in water to give a clear solution, yields the initial insoluble pigment upon hydrolysis with dilute alkalis.

Example 13 22.6 parts of the anhydrous disodium salt of furane-Z-carboxylic acid-3-su1fonic acid [prepared as described by Hill and Palmer, Proceedings of the American Academy, vol. 23, page 214 (1888)] are mixed with 120 parts by volume of dry pyridine while stirring, 18.4 parts of paratoluene sulfochloride are added, and then 10.0 parts of the azo dyestuif from 3-chloro-l-aminobenzene and 1- (2-hydroxy-3-naphthoylamino) 2-methylbenzene are introduced. The reaction mixture is heated to -80" C. while stirring for 40-80 minutes, and then refluxed for a short time in an oily bath. A test portion will then be soluble in water. The reaction mixture is cooled to room temperature, and stirred into a mixture of 450 parts of water and 63 parts of concentrated sulfuric acid, 60 parts of sodium chloride are added,

13 and the whole is heated to 40-50 (1, whereupon the reaction product separates well in the form of a resinous deposit. After-pouringiofithe liquor containing sulfuric acid and p id ilr'iefsulfate, the residue is dissolved in 500 fiaxgtsof water while heating at 40-50 0., filtered 'wlthsuction, salted out with 60 parts of sodium chloride .at40-50 0., the salt solution is separatedand the reaction product is then dried in vacuo at 40 50 C. The orange-brown water-soluble reaction product yields the initial insoluble pigmentwen hydrolysis with dilute alkalis.

Example 14 29.3 parts of the anhydrous disodium salt of 3:4 dichlorofurane 2 -carbox*y1ic acid sulfonic acid [prepared as described by Hill and Hendrixson, American Chemical Journal, vol. 15, page 149 (1893)] are mixed with 120 parts by volume of dry pyridine while stirring, 22.6 parts of para-toluene sulfochlorideareadded,,and then 10.0 parts of the azo dyest'ufi from diazotized B-chloro-l-aminobenzne and 2 hydroxy-3- naphthoylamino) 2 methy nz'ene are introduced. The reaction mixtuii eated at 75-80 C. for 40-80 minutes while s ngfand then refiuxed for a short time in an ily bath. A test portion is then soluble in water. The reaction mixture is cooled to room temperature, "stirred into a mixture of 450 parts of .water'and' 63 parts of concentrated sulfuric acid, 60 parts of sodium chloride are added, and the whole is heated to 40-50 0., whereupon the reaction product separates in the form of a resinous deposit. After pouring off the liquor containing sulfuric acid and pyridine sulfate,the residue is dissolved in ""14 500 parts of water while heating at -50 'C., filtered with suction, salted out with parts of sodium chloride at 40-50 C., the salt solution is separated, and the reaction product is then dried in vacuo at 40-50 C. The orange-brown watersolublereaction product yields the initial insoluble pigment upon hydrolysis with dilute alkalis.

Example 15 4 parts of furai'ie-2-carlf:oxylic acid-5 sulfonic acid are dissolved in 40 parts of dry pyridine and 5.7 parts of para toluenesulfobromide are added. 2 parts of the azo dyestufi from diazotiz'ed 3- chloro-l-aminobenzene and 1-(2'-hydroxy-3 naphthoylamino) -2-methylbenzene are. added to the reaction mixture, and the latter is then heated to 95 C. while stirring. After about hour, the pigment will have dissolved in the reaction mixture and a test portion of the dark yellowbrown solution will be soluble in water to give a clear solution. The reaction mixture is'cooled to room temperature and introduced into dilute sulfuric acid, and completely"precipitatedby the addition of sodium chloride. After separating the liquor containing sulfuric and and pyridine sulfate, and drying in vacuo at 40-50 Q, the reaction product is obtained in the form of an orangebrown powder which dissolves in water to give a clear solution having an-orange-brown coloration, and can be hydrolyzed rapidly with dilute alkalis to yield the initial insoluble pigment.

In the following table is given a list of further valuable azo-dyestuff derivatives which can be made by the present process by acylating the azodyestufi mentioned in column Iwith theacylating agent mentioned in column II:

I II III IV Mame Color of the xz'oaiyestun Acylating Agent 231 1 23 2 product of compound hydrolysis (l) :Diaz. l-ehloroq fiiethyld aminobenzene Furane-2-carboxylic acidred-brown red.

.1 -.(2. -hydroxy-3'- naphthoylamino) 2- methyli- 5-sulfonic acicH-phosolildobeliz'e'fie. j gene in pyridine. g

(2) Difizi BililfiviO-biitriinbbfliene 1-(2-hydo orange-brown. orange-red. dmXy-W-nephthoylarnino) 21methoxybenzene. 4

(3) Dia z. 2 3 5 616211oi'o l arnfiioben'zene l-(2- Furane-fl-carboigyhc, ae d- .-.do scarlet.

fiydroXy-3-naphthoylamino)#methylbenzene. 5 sulfonic acid paratoluene-sulfochloride in I pyridine. (4) Dias:fi oliloi-ofi-uietlibiry l-aminobenzene-- do red-brown..." red.

1- (2 h'ydroxy 3' naphthoylamino) 2 methoxybenieiie. l. (5)"Dia'z. '2:5 dicliloro-laminobenzene 1-(2- .do yellow-brown. brown.

hydroxy 3'--naphthoylamino) 2:5 dimethoxybenzene. I (6) Dias."4 nitlioiy-wnitro-1=aminobenzene do brown bordeaux.

(2,- hydroxy- 3"- naphthoylamino) 2- methoxyenzen .l (7)Diz; l nitlo-z rfietliyl-l-aininobenzene do i orange-brown. ruby.

l3 ydroxy 3' naphthoylamino)-2 methoxy- (8)'Dian $A-nitro-irinethyl-baminobenzene -v do red-brown-.. Do.

1- (2'-hydroxy-3'-naphthoylamino) 2 methylbenzene. (9) Didi. 5-trifluoromethyl-2-chloro-l-a1ninobenzene do yellow-brown. orange.

1-(2'-hydroxy-3-naphthoylamino)-2-methqoxybemana ,4

0).Dla 5 uoromethyl-2-chloro-1-ammobendo .do Do. 'l (2 hydroxy-3-ne.phthoylamino)- Y 2-inethyl-l-aminobenzene do orange-brown. scarlet.

' naphthoylamino) 2 ethoxyltro-lqiininobenzene 1-(2- red-brownunnred. I 4. y :3'fnanhthoylamino)-naohthalene.

(l3) 'Diaz.- 5-ohlorog2-methyl-l-aminobenzene do... Do.

142' hydlbiy 3' naphthoylamino) 2-metl1 mane... m. I, (14)Dia -4-chloro-2-methyl-l-aminobenzene ...-do Do.

d'fxT-B naphthoylamino)-2-methylbhl'eh'e. (l5) Diaz. ,fl-nitro-l-aminobenzene --v l-(2-hybrown Do.

drOicy-W-naphtlioyhflxino)-2-methylbenzene. (l6) Diaz. 2:fi-dicliloxo l-aminobenzene 1- orange-brown scarlet.

(2-hydroxy-3'-naphthoylamino)-benzene. (l7) Diaz.4:4dich1or0-2-amilio diphenyl ether ..do red.

1 (2' -hydroxy 3' maphthoylarnino) 2-meth0xybenzene.

I II III IV Colorofaque- C olor of the Azo-dyestufi Acylating Agent g ggg? product of compound hydrolysis (18)Diaz. 2:5-dich10rol'aminobenzene L Furane-Z-carboxylic aciddo orange.

(2-hydroxy3-naphthoylamino)-2-ehlorobenzene. 2-sulfon1cacid-l-paratoluene sulfochloride in pyridine. Diaz. 3-chloro-1-aminobenzeue l-(2-hydo yellow-brown. Do.

droxy-3-naphthoylamino)-benzene. Diaz. 2:5-dichloro-1-aminobenzene l-(2- do orange-browm scarlet.

hydroxy-3-nnphthoylamino)-3-chlorobenzene. (21) Diaz. 3-chloro-laminobenzene -v 1(2-hy- .do yellow-brown. Do.

droxy-3-naphthoylamino) -2-methoxy-5 chlorobenzene. (22) Diaz. 4-chloro-2-aminodiphenyl ether l- .do orange-brown. red.

(2-hydroxy-3-naphthoylamiuo)-benzene. (23) Diaz. 4-nitro-2-methyl-l-aminobenzene ..do orange brown.

NH OH 31 The acyl compounds corresponding to items 6, 9, 13 and 14 of the foregoing table correspond to the following formulae:

0 Example 16 A dyebath is prepared which consists of 5 parts of the product of the action of furane-Z-carboxylic aoid-5-sulfonic acid and phosgene on the azo dyestufi from diazotized 2:5 dichloro 1- aminobenzene and 1-(2'-hydroxy3-naphthoylamino) 2 methoxybenzene (according to Example 4), 3000 parts of water and 50 parts of sulfuric acid of 10 per cent. strength. parts of a wool fabric are entered at 40 C., the dyebath is then slowly raised to the boil in the course of 1 hour, and finally boiling is continued for a further /2 hour. During this period the dyestufl derivative is taken up completely by the wool and an orange-red dyeing is obtained. The dyeing is then developed at room temperature in an ammonia solution of 1 per cent. strength for about 5 minutes, rinsed, soaped for 10 minutes at 50 C. with a solution containing, per litre of water, 2 grams of the sodium salt of N-benzyl-heptadecylbenzimidazole disulfonic acid, again rinsed, and dried. In this manner a strong brilliant scarlet dyeing having good to excellent properties 0! fastness is obtained.

Example 17 A printing paste is prepared consisting of 70 parts of the product obtainable as described in Example 4 by the action of furane-Z- carboxylic acid-5-sulfonic acid and phosgene on the azo-dyestuff from diazotized 2 5-dichloro-1-aminobenzene and 1- (2'- hydroxy 3 naphthoylamino) 2- methoxybenzene, 330 parts of water, 100 parts of thiodiglycol, 500 parts of neutral starch-tragacanth thickening 1000 parts.

The above printing color is printed on a cotton fabric, and the print is dried and steamed for -10 minutes in a Mather-Flatt apparatus. print is then developed by a short passage (about 1-2 minutes) through an ammonia solution of 1-2 per cent. strength, and then malted and soaped at the boil. In this manner a fast brilliant scarlet print is obtained.

The

What we claim is: 1. An azo dyestuff derivative of the formula (NE -H 0-o C-A-S 03H in which n and m represent whole numbers, the sum of which is at most 3, R2 represents the radical of a diazo component, and A represents a five membered heterocyclic ring consisting of 4 carbon atoms bound together by conjugate double bonds and one atom selected from the group consisting of oxygen and sulfur, and which azo dyestuff derivative contains a single CON-group and is free from substituents imparting solubility apart from the indicated sulfonic acid groups.

2. An azo dyestufi derivative of the formula in which R2 represents a benzene radical and R3 represents a benzene radical, and which azo dyestuff derivative contains a single CO-N-group and is free from substituents imparting solubility apart from the indicated sulfonic acid groups.

3. The azo dyestufi derivative of the formula HC--CH -SOaH 0 4. The azo dyestufi derivative of the formula 6. The azo dyestufi derivative of the formula 7. The azo dyestufi derivative of the formula CHARLES GRAENACHER. HEINRICH BRUENGGER. ADOLF EMIL SIEGRIST.

References Cited in the file of this patent UNITED STATES PATENTS Number Name Date Zwilgmeyer Dec. 15, 1936 Markush Mar. 16, 1937 Graenacher et a1. Mar. 10, 1942 

2. AN AZO DYESTUFF DERIVATIVE OF THE FORMULA 